Processing apparatus equipped with catalyst-supporting honeycomb structure, and method for manufacturing same

ABSTRACT

A processing apparatus equipped with a catalyst-supporting honeycomb structure, which is characterized in that corrugated plate-like glass fiber papers having a functional catalyst supported thereon and flat plate-like glass fiber papers having the same functional catalyst supported thereon are alternately laminated without being bonded to each other, to form a catalyst-supporting honeycomb structure, and this catalyst-supporting honeycomb structure is packed in a casing.

TECHNICAL FIELD

The present invention relates to a processing apparatus equipped with acatalyst-supporting honeycomb structure which is used for, for example,an exhaust gas cleaning process or manufacture of hydrogen by ammoniadecomposition, or the like, and a method for manufacturing the same.

BACKGROUND ART

Conventionally, as a base material of a honeycomb structure (flatplate+corrugated plate) of a processing apparatus equipped with acatalyst-supporting honeycomb structure which is used for an exhaust gascleaning process or the like, it was difficult to use commerciallyavailable glass fiber papers, and glass fiber papers which areapplicable to corrugate processing were restricted with respect to thekinds thereof (see Patent Literature 1 as described below).

Then, conventionally, in order to fabricate the processing apparatusequipped with a catalyst-supporting honeycomb structure, a tangentportion of the honeycomb structure, namely a portion in which apexes ofthe corrugated plate come into contact with the flat plate, was bondedvia an adhesive, and for the purpose of keeping the honeycomb structure,other means were not taken.

In addition, in the manufacture of an exhaust gas cleaning processingapparatus including a conventional honeycomb structure as a basematerial, in order to support a functional catalyst on the honeycombstructure, a method of dipping the honeycomb structure itself in acatalyst-containing solution or slurry was adopted.

Furthermore, in this honeycomb structure formed by alternatelylaminating flat plates and corrugated plates and bonding, for example,in the case where a solid content is contained in a gas to be processedin an exhaust gas cleaning process or the like, there is seen aphenomenon in which the solid content clogs in cells (voids) of thehoneycomb structure with a lapse of operating time. Since the gas to beprocessed does not come into contact with inner walls of the cellsclogged with the solid content, a contact area of the gas to beprocessed is lowered. In addition, a pressure loss increases. Inconsequence, in the case of clogging is generated to a certain extent ormore by an exhaust gas cleaning process or the like, it was necessary toexchange the honeycomb structure or conduct a regeneration process forresolution of clogging.

Conventionally, as for such a regeneration process for resolution ofclogging of the honeycomb structure, there was adopted a method ofpressing the clogged portion by a stick or the like.

PRIOR ART LITERATURE Patent Literature

PTL 1: JP-A-2010-013773

SUMMARY OF INVENTION Technical Problem

However, according to the conventional method described in theabove-described Patent Literature 1, in order to support the catalyst onthe honeycomb structure, the honeycomb structure itself is dipped in acatalyst-containing solution or slurry and then dried. For this reason,large-scale equipment was required as a dipping tank of the honeycombstructure or a drying device, and in its turn, there was involved such aproblem that the manufacturing cost of the honeycomb structure is high.

In addition, according to the conventional method, for example, as forthe regeneration process for resolution of clogging of cells of thehoneycomb structure with a solid content in the gas to be processed inan exhaust gas cleaning process or the like, a method of pressing theclogged portion by a stick or the like is adopted. Therefore, in ahoneycomb structure with poor mechanical strength, there was involvedsuch a problem that the cell portions are damaged by such a regenerationprocess.

An object of the present invention is to solve the above-describedproblems of the conventional art and to provide a processing apparatusequipped with a catalyst-supporting honeycomb structure, as well as amethod for manufacturing the same, in which the catalyst-supportinghoneycomb structure can be formed by using a commercially available,inexpensive glass fiber paper as a base material; the manufacturing costis low without requiring large-scale equipment such as a dipping tank, adrying device, etc. as conventionally used for a catalyst-supportinghoneycomb structure; for example, in an exhaust gas cleaning process orthe like, even if a solid content in a gas to be processed clogs incells of the catalyst-supporting honeycomb structure with a lapse ofoperating time, this can be easily regenerated; and a lowering of acontact area of the gas to be processed or an increase of a pressureloss can be prevented from occurring.

Solution to Problem

In order to solve the above-described problem, an invention as set forthin claim 1 is concerned with a processing apparatus equipped with acatalyst-supporting honeycomb structure, which is characterized in thatcorrugated plate-like glass fiber papers having a functional catalystsupported thereon and flat plate-like glass fiber papers having the samefunctional catalyst supported thereon are alternately laminated withoutbeing bonded to each other, to form a catalyst-supporting honeycombstructure, and this catalyst-supporting honeycomb structure is packed ina casing.

An invention as set forth in claim 2 is concerned with the processingapparatus equipped with a catalyst-supporting honeycomb structureaccording to claim 1, which is characterized in that the casing has asquare cylindrical shape, and the casing is composed of a casing mainbody having a lateral cross section of a substantially U-shape and aflat plate-like lid body that covers an opening of this, or composed ofa casing main body having a lateral cross section of a substantiallyL-shape and a lid body to be fitted into this and having a lateral crosssection of a substantially inverted L-shape.

An invention as set forth in claim 3 is concerned with the processingapparatus equipped with a catalyst-supporting honeycomb structureaccording to claim 1 or 2, which is characterized in that an inorganicfiber blanket is laid on an inner surface of the casing.

An invention as set forth in claim 4 is concerned with the processingapparatus equipped with a catalyst-supporting honeycomb structureaccording to anyone of claims 1 to 3, which is characterized in that thefunctional catalyst is a catalyst selected from the group consisting ofa denitration catalyst, a desulfurization catalyst, a dioxindecomposition catalyst, and an ammonia decomposition catalyst, and isused for an exhaust gas cleaning process or manufacture of hydrogen byammonia decomposition.

An invention as set forth in claim 5 is concerned with a method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure, which is characterized by consisting of a step ofbaking a glass fiber paper to remove an organic binder componentcontained in the glass fiber paper by burning; a step of applying afunctional catalyst-containing slurry on the glass fiber paper afterremoval of the organic binder component; a step of shaping thefunctional catalyst-containing slurry-applied glass fiber paper by acrimping die and a pressing jig; a step of drying the shaped, corrugatedplate-like functional catalyst-containing slurry-applied glass fiberpaper and peeling off it from the die; meanwhile, a step of drying theflat plate-like functional catalyst slurry-applied glass fiber paperhaving not been shaped in a corrugated plate-like form; a step ofcalcinating the corrugated plate-like functional catalyst-containingslurry-applied glass fiber paper and the flat plate-like functionalcatalyst slurry-applied glass fiber paper to form a functionalcatalyst-supporting, flat plate-like glass fiber paper and a functionalcatalyst-supporting, corrugated plate-like glass fiber paper; and a stepof alternately laminating the functional catalyst-supporting, flatplate-like glass fiber paper after calcination and the functionalcatalyst-supporting, corrugated plate-like glass fiber paper aftercalcination without being bonded to each other, to form acatalyst-supporting honeycomb structure and packing thiscatalyst-supporting honeycomb structure in a casing.

An invention as set forth in claim 6 is concerned with the method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to claim 5, which is characterized in thatthe removal step of an organic binder component of the glass fiber paperis carried out under a baking condition at from 350 to 450° C. for from30 minutes to one hour and thirty minutes.

An invention as set forth in claim 7 is concerned with the method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to claim 5 or 6, which is characterized inthat in the applying step of a functional catalyst-containing slurry, afunctional catalyst-containing slurry in which a silica sol is containedis used.

An invention as set forth in claim 8 is concerned with the method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to any one of claims 5 to 7, which ischaracterized in that in the shaping step of the functional catalystslurry-applied glass fiber paper in a corrugated plate-like form, a diecomposed of a metal panel having parallel recessed grooves having awidth of from 5 to 15 mm, a height of from 2 to 10 mm, and a radius ofcurvature in a groove bottom of from 0.5 to 2 mm is used, and thefunctional catalyst slurry-applied glass fiber paper placed on the dieis pressed down along the recessed grooves of the die by the pressingjig, thereby achieving shaping.

An invention as set forth in claim 9 is concerned with the method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to any one of claims 5 to 8, which ischaracterized in that the drying steps of the shaped, corrugatedplate-like functional catalyst-containing slurry-applied glass fiberpaper and the flat plate-like functional catalyst slurry-applied glassfiber paper having not been shaped in a corrugated plate-like form arecarried out under a condition at from 250 to 400° C. for from 30 minutesto one hour and thirty minutes, respectively.

An invention as set forth in claim 10 is concerned with the method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to any one of claims 5 to 9, which ischaracterized in that the calcination step of the corrugated plate-likefunctional catalyst-containing slurry-applied glass fiber paper and theflat plate-like functional catalyst slurry-applied glass fiber paper asformed in a honeycomb structure is carried out under a condition at from400 to 550° C. for 2 to 4 hours.

An invention set forth in claim. 11 is concerned with the method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to anyone of claims 5 to 10, which ischaracterized in that in the packing step of the catalyst-supportinghoneycomb structure, the inorganic fiber blanket is laid on an innersurface of the casing before packing of the catalyst-supportinghoneycomb structure.

Advantageous Effects of Invention

According to the invention as set forth in claim 1, there are broughtsuch effects that the catalyst-supporting honeycomb structure can beformed by using a commercially available, inexpensive glass fiber paperas a base material; the manufacturing cost is low without requiringlarge-scale equipment such as a dipping tank, a drying device, etc. asconventionally used for a honeycomb structure; for example, in anexhaust gas cleaning process or the like, even if a solid content in agas to be processed clogs in cells of the catalyst-supporting honeycombstructure with a lapse of operating time, this can be easilyregenerated; and a lowering of a contact area of the gas to be processedor an increase of a pressure loss can be prevented from occurring.

According to the invention as set forth in claim 2, there are broughtsuch effects that the inexpensive catalyst-supporting honeycombstructure using a glass fiber paper as a base material can be stablykept; and the casing can be opened for the purpose of resolution ofclogging of cells of the catalyst-supporting honeycomb structure to becaused due to a solid content in a gas to be processed in an exhaust gascleaning process or the like.

According to the invention as set forth in claim 3, there is broughtsuch an effect that a vibration countermeasure can be taken by africtional force by the catalyst-supporting honeycomb structure and theinorganic fiber blanket.

According to the invention as set forth in claim 4, there is broughtsuch an effect that the inexpensive catalyst-supporting honeycombstructure using a glass fiber paper as a base material can be utilizedfor an exhaust gas cleaning process and manufacture of hydrogen byammonia decomposition.

According to the invention as set forth in claim 5, there are broughtsuch effects that the catalyst-supporting honeycomb structure can beformed by using a commercially available, inexpensive glass fiber paperas a base material; the manufacturing cost is low without requiringlarge-scale equipment such as a dipping tank, a drying device, etc. asconventionally used for a honeycomb structure; for example, in anexhaust gas cleaning process or the like, even if a solid content in agas to be processed clogs in cells of the catalyst-supporting honeycombstructure with a lapse of operating time, this can be easilyregenerated; and a lowering of a contact area of the gas to be processedor an increase of a pressure loss can be prevented from occurring.

According to the invention as set forth in claim 6, there are broughtsuch effects that by baking the glass fiber paper, it is possible toremove the organic binder with ease; since the glass fiber paper afterremoval of the organic binder loses a force of repulsion, it is possibleto conduct molding in a corrugated form, so that the catalyst-supportinghoneycomb structure can be formed by using a glass fiber paper as a basematerial; and moreover, the manufacturing cost is low without requiringlarge-scale equipment.

According to the invention as set forth in claim 7, there is broughtsuch an effect that by applying the silica sol-containing functionalcatalyst on the glass fiber paper which has lost a force of repulsion byremoval of the organic binder in the baking step, the silica solexhibits a function as an inorganic binder, thereby keeping the shape ofa functional catalyst-supporting glass fiber paper.

According to the invention as set forth in claim 8, there is broughtsuch an effect that it is possible to conduct molding in a corrugatedplate-like form without causing breakage of the functionalcatalyst-supporting glass fiber paper.

According to the invention as set forth in claim 9, there is broughtsuch an effect that the corrugated plate-like and flat plate-likefunctional catalyst slurry-applied glass fiber papers can be peeled offfrom the die with ease upon drying.

According to the invention as set forth in claim 10, there is broughtsuch an effect that uniform calcination can be conducted without causinga decrease of activity of the functional catalyst.

According to the invention as set forth in claim 11, there is broughtsuch an effect that a vibration countermeasure can be taken by africtional force by the catalyst-supporting honeycomb structure and theinorganic fiber blanket.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a perspective view showing an embodiment of a processingapparatus equipped with a catalyst-supporting honeycomb structureaccording to the present invention.

FIG. 2 is a principal part, enlarged front view of a catalyst-supportinghoneycomb structure portion of the processing apparatus of FIG. 1.

FIG. 3 is a block diagram showing sequent steps of a method formanufacturing a processing apparatus equipped with a catalyst-supportinghoneycomb structure according to the present invention.

EXPLANATIONS OF REFERENCE NUMERALS

-   -   1: Catalyst-supporting honeycomb structure    -   2: Functional catalyst-supporting, corrugated plate-like glass        fiber paper    -   3: Functional catalyst-supporting, flat plate-like glass fiber        paper    -   4: Casing    -   4 a: Casing main body    -   4 b: Lid body    -   5: Blanket    -   10: Processing apparatus equipped with a catalyst-supporting        honeycomb structure

DESCRIPTION OF EMBODIMENTS

Next, embodiments of the present invention are described by reference tothe accompanying drawings, but it should not be construed that thepresent invention is limited thereto.

FIG. 1 is a perspective view showing an embodiment of a processingapparatus equipped with a catalyst-supporting honeycomb structureaccording to the present invention. FIG. 2 is a principal part, enlargedfront view of a catalyst-supporting honeycomb structure portion of theprocessing apparatus of FIG. 1.

Referring to FIGS. 1 and 2, a processing apparatus (10) equipped with acatalyst-supporting honeycomb structure according to the presentinvention is characterized in that a corrugated plate-like glass fiberpaper (2) having a functional catalyst supported thereon and a flatplate-like glass fiber paper (3) having the same functional catalystsupported thereon are alternately laminated without being bonded to eachother, to form a catalyst-supporting honeycomb structure (1), and thiscatalyst-supporting honeycomb structure (1) is packed in a casing (4).

The present inventors noted that a reason why a commercially availableglass fiber paper cannot be molded in a corrugated plate-like form byusing a corrugation molding machine (corrugator) resides in the matterthat a force of repulsion due to an organic binder contained in theglass fiber paper is so large that even if the glass fiber paper is bentby applying a force, it is returned into an original state, whereas if aforce is excessively applied, the glass fiber paper breaks, andtherefore, a large force cannot be applied. However, it has been foundthat it is possible to remove an organic binder contained in a glassfiber paper with ease by baking the glass fiber paper, and since theglass fiber paper after removal of the organic binder loses a force ofrepulsion, it is possible to mold the glass fiber paper in a corrugatedform. Furthermore, when a functional catalyst-containing slurry isapplied on the glass fiber paper after baking, an inorganic bindercontained in the slurry, for example, a silica sol, etc., carries out afunction as a binder of the glass fiber paper, and by applying afunctional catalyst-containing slurry on the glass fiber paper afterbaking, it is possible to keep the corrugated form. In this way, it hasbeen found that the catalyst-supporting honeycomb structure (1) that isa laminate of the functional catalyst-supporting, flat plate-like glassfiber paper (3) and the functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) can be manufactured without bondingflat plates and corrugated plates each using a glass fiber paper to eachother with an adhesive as in the conventional art.

In accordance with the processing apparatus (10) equipped with acatalyst-supporting honeycomb structure according to the presentinvention, the catalyst-supporting honeycomb structure (1) can be formedby using a commercially available, inexpensive glass fiber paper as abase material. Moreover, since it is merely required that a functionalcatalyst-containing slurry is applied on the glass fiber paper afterremoval of the organic binder component and then dried, themanufacturing cost is low without requiring large-scale equipment suchas a dipping tank, a drying device, etc. as conventionally used for aso-called adhesive type honeycomb structure.

In addition, for example, in an exhaust gas cleaning process or thelike, even if a solid content in a gas to be processed clogs in cells ofthe catalyst-supporting honeycomb structure (1) with a lapse ofoperating time, since the functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) and the functional catalyst-supporting,flat plate-like glass fiber paper (3) are alternately laminated withoutbeing bonded to each other, to form the catalyst-supporting honeycombstructure (1), and this catalyst-supporting honeycomb structure (1) ispacked in the casing (4), these can be discharged separately from thecasing (4), the functional catalyst-supporting, corrugated plate-likeglass fiber paper (2) and the functional catalyst-supporting, flatplate-like glass fiber paper (3) as discharged can be easily regeneratedby means of cleaning or the like. Therefore, a lowering of a contactarea with the gas to be processed or an increase of a pressure loss canbe surely prevented from occurring.

In the processing apparatus (10) equipped with a catalyst-supportinghoneycomb structure according to the present invention, it is preferablethat the casing (4) has a square cylindrical shape. It is preferablethat the casing (4) is composed of a casing main body (4 a) having alateral cross section of a substantially U-shape and a flat plate-likelid body (4 b) that covers an opening of this.

Also, while illustration is omitted, it is preferable that the casing(4) is composed of a casing main body having a lateral cross section ofa substantially L-shape and a lid body to be fitted into this and havinga lateral cross section of a substantially inverted L-shape.

It is to be noted that the shape of the casing (4) is not limited to asquare cylindrical shape, but it may also be a cylindrical shape.However, the square cylindrical shape is more preferable on the occasionof packing the casing (4) with the catalyst-supporting honeycombstructure (1) in which the functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) after baking and the functionalcatalyst-supporting, flat plate-like glass fiber paper (3) after bakingare alternately laminated without being bonded to each other.

In the processing apparatus (10) equipped with a catalyst-supportinghoneycomb structure according to the present invention, it is preferablethat an inorganic fiber blanket (5) is laid on an inner surface of thecasing (4). A vibration countermeasure can be taken by a frictionalforce by the catalyst-supporting honeycomb structure (1) and theinorganic fiber blanket (5) on the inner surface of the casing (4).

Here, examples of an inorganic fiber that is a raw material of theblanket (5) include a ceramic fiber, a glass fiber, a silica sol fiber,an alumina fiber, and a rock wool.

In addition, in the processing apparatus (10) equipped with acatalyst-supporting honeycomb structure according to the presentinvention, the functional catalyst is preferably a catalyst selectedfrom the group consisting of a denitration catalyst, a desulfurizationcatalyst, a dioxin decomposition catalyst, and an ammonia decompositioncatalyst, and it can be used for an exhaust gas cleaning process ormanufacture of hydrogen by ammonia decomposition. It is to be noted thata catalyst containing vanadium is preferably used as the denitrationcatalyst, and a catalyst containing ruthenium is preferably used as theammonia decomposition catalyst.

Next, a method for manufacturing the processing apparatus (10) equippedwith a catalyst-supporting honeycomb structure according to the presentinvention is described. FIG. 3 is a flow sheet showing sequent steps ofthe manufacture method according to the present invention.

Referring to this drawing, the method for manufacturing the processingapparatus (10) equipped with a catalyst-supporting honeycomb structureaccording to the present invention consists of a step of baking acommercially available glass fiber paper to remove an organic bindercomponent contained in the glass fiber paper by burning; a step ofapplying a functional catalyst-containing slurry on the glass fiberpaper after removal of the organic binder component; a step of shapingthe functional catalyst-containing slurry-applied glass fiber paper by acrimping die and a pressing jig; a step of drying the shaped, corrugatedplate-like functional catalyst-containing slurry-applied glass fiberpaper and peeling off it from the die; meanwhile, a step of drying theflat plate-like functional catalyst slurry-applied glass fiber paperhaving not been shaped in a corrugated plate-like form; a step ofcalcinating the corrugated plate-like functional catalyst-containingslurry-applied glass fiber paper and the flat plate-like functionalcatalyst slurry-applied glass fiber paper to form the functionalcatalyst-supporting, flat plate-like glass fiber paper (2) and thefunctional catalyst-supporting, corrugated plate-like glass fiber paper(3); and a step of laying an inorganic fiber blanket (5) in the casing(4), alternately laminating the functional catalyst-supporting, flatplate-like glass fiber paper (2) after calcination and the functionalcatalyst-supporting, corrugated plate-like glass fiber paper (3) aftercalcination without being bonded to each other, to form thecatalyst-supporting honeycomb structure (1) and packing thiscatalyst-supporting honeycomb structure (1) in the casing (4).

That is, a commercially available glass fiber paper containing anorganic binder can be used for the glass fiber paper which is used inthe present invention. It is to be noted that examples of the organicbinder which is used in the commercially available glass fiber paperinclude an acrylic resin, a polyvinyl alcohol (PVA)/polyvinyl acetatecopolymer, an unsaturated polyester-based resin, an epoxy resin, and thelike.

Then, in the method for manufacturing the processing apparatus (10)equipped with a catalyst-supporting honeycomb structure according to thepresent invention, it is preferable that the removal step of an organicbinder component of the glass fiber paper is carried out under a bakingcondition at from 350 to 450° C. for from 30 minutes to one hour andthirty minutes.

Here, when the baking temperature is made too high, or the baking timeis made too long, the organic binder contained in the glass fiber paperis excessively removed, so that the shape of the glass fiber papercannot be kept. On the other hand, when the baking temperature is toolow, or the baking time is too short, the organic binder does not blow,namely it cannot be removed, and hence, such is not preferable.

Meanwhile, in order to obtain the flat plate-like functionalcatalyst-supporting glass fiber paper having not been shaped in acorrugated plate-like form, at first, a commercially available glassfiber paper having necessary width and length is cut out from a roll;however, finally, the flat plate-like functional catalyst-supportingglass fiber paper (3) to be packed in the casing (4) may be made to havethe same size as that of the corrugated plate-like functionalcatalyst-supporting glass fiber paper (2) as seen from the plane.

In the applying step of a functional catalyst-containing slurry in themethod for manufacturing the processing apparatus (10) equipped with acatalyst-supporting honeycomb structure according to the presentinvention, the functional catalyst-containing slurry to be applied onthe glass fiber paper after removal of the organic binder component ispreferably one containing a functional catalyst in which a silica sol iscontained. This is because by applying the functionalcatalyst-containing slurry in which a silica sol is contained on theglass fiber paper after removal of the organic binder, the silica solcarries out a function as an inorganic binder and keeps the shape. It isto be noted that so long as a silica sol content in the functionalcatalyst is from 10 to 30% by weight, not only a mechanical structurebut a catalytic performance can be stably exhibited, and hence, such ispreferable. However, it should not be construed that the presentinvention is limited thereto. The functional catalyst-containing slurryin which a silica sol is contained is one containing the functionalcatalyst selected from the group consisting of a denitration catalyst, adesulfurization catalyst, a dioxin decomposition catalyst, and anammonia decomposition catalyst, and the inexpensive catalyst-supportinghoneycomb structure (1) using a commercially available glass fiber paperas a base material can be utilized for an exhaust gas cleaning processand manufacture of hydrogen by ammonia decomposition.

Here, for example, as the denitration catalyst, a denitration catalystdescribed in JP-A-2008-155133 by the present applicant can be used. Inthis denitration catalyst-containing slurry, a silica sol (Si) that is abinder component and titanium (Ti), vanadium (V), and tungsten (W) thatare denitration catalyst metals are contained. In addition, as theammonia decomposition catalyst, an ammonia decomposition catalystdescribed in JP-A-2011-78888 can be used. In the ammonia decompositioncatalyst, ruthenium (Ru) that is an ammonium decomposition catalystmetal and a promoter are contained, and this ammonia decompositioncatalyst can be utilized as the functional catalyst in the presentinvention when this catalyst contains a silica sol (Si) thereon.

That is, for example, the denitration catalyst-containing slurry isobtained by adding ammonium metavanadate to a slurry of titania fineparticles suspended in a silica sol to adsorb titania thereon andfurther adding ammonium metatungstate or an aqueous solution thereof.Then, this denitration catalyst-containing slurry is applied on theabove-described glass fiber paper after removal of the organic bindercomponent and then dried, thereby simultaneously supporting titania,vanadium oxide, and ammonium metatungstate on the glass fiber paper.According to this, supporting of titania, supporting of vanadium, andsupporting of tungsten can be conducted at the same time in one step. Inconsequence, the operation of applying, drying and calcinating may be aone-time operation, and a decrease of the number of steps, anenhancement of productivity, and a reduction of cost can be achieved.

In the step of applying the functional catalyst-containing slurry fordenitration or the like on the glass fiber paper after removal of theorganic binder component and then drying to support the functionalcatalyst on the glass fiber paper, as a applying method, it is possibleto adopt any applying method, for example, a so-called dipping method, abrush coating method, a spray coating method, a drip coating method,etc.

Now, a reason why the glass fiber paper cannot be molded in a corrugatedplate-like form by using a corrugation molding machine (corrugator)resides in the matter that a force of repulsion due to an organic bindercontained in the glass fiber paper is so large that even if the glassfiber paper is bent by applying a force, it is returned into an originalstate. In addition, if a force is excessively applied, the glass fiberpaper breaks, and therefore, a large force cannot be applied.

However, it is possible to remove the organic binder with ease by bakingthe glass fiber paper. In addition, since the glass fiber paper afterremoval of the organic binder loses a force of repulsion, it can bemolded in a corrugated plate-like form. Furthermore, when the functionalcatalyst-containing slurry is applied on the glass fiber paper afterbaking, the inorganic binder contained in the slurry, for example, asilica sol, etc., carries out a function as a binder of the glass fiberpaper, and by applying the functional catalyst-containing slurry on theglass fiber paper after baking, it is possible to keep the corrugatedform. In this way, it has become possible to manufacture the honeycombstructure (1) that is a laminate of a flat plate and a corrugated plateby the functional catalyst-supporting flat plate and the functionalcatalyst-supporting corrugated plate each utilizing a glass fiber paperwithout bonding with an adhesive as in the conventional art.

In the shaping step of the functional catalyst slurry-applied glassfiber paper in a corrugated plate-like form in the method formanufacturing the processing apparatus (10) equipped with acatalyst-supporting honeycomb structure according to the presentinvention, it is preferable that a die composed of a metal panel havingparallel recessed grooves having a width of from 5 to 15 mm, a height offrom 2 to 10 mm, and a radius of curvature in a groove bottom of from0.5 to 2 mm is used, and the functional catalyst slurry-applied glassfiber paper placed on the die is pressed down along the recessed groovesof the die by a pressing jig, thereby achieving shaping.

In the pressing jig, a portion that comes into contact with the glassfiber paper is subjected to water repellent finishing, namely TEFLON(registered trademark) finishing. Unless the recessed grooves of thecorrugated plate-like die at the lower side of the glass fiber paper tobe pressed down have a shape having a radius of curvature of from about0.5 to 2 mm, pressing-down cannot be achieved, and if the radius ofcurvature is smaller than this, the glass fiber paper breaks, and hence,such is not preferable.

In the method for manufacturing the processing apparatus (10) equippedwith a catalyst-supporting honeycomb structure according to the presentinvention, it is preferable that the drying steps of the shaped,corrugated plate-like functional catalyst-containing slurry-appliedglass fiber paper and the flat plate-like functional catalystslurry-applied glass fiber paper having not been shaped in a corrugatedplate-like form are carried out under a condition at from 250 to 400° C.for from 30 minutes to one hour and thirty minutes, respectively.According to this, it is possible to dry the corrugated plate-like andflat plate-like functional catalyst slurry-applied glass fiber paperswithout causing a decrease of activity of the functional catalyst suchas a denitration catalyst, etc. In addition, the thus dried, corrugatedplate-like functional catalyst-containing slurry-applied glass fiberpaper can be peeled off from the die with ease.

Here, it is to be noted that in order to surely peel off the shaped,corrugated plate-like functional catalyst-containing slurry-appliedglass fiber paper from the die, the drying time and management of thedie are important.

First of all, as for the drying temperature and time, it is preferableto dry the catalyst at a temperature of from 250 to 400° C. for a timeof from 30 minutes to hour and thirty minutes. For example, if drying isconducted at a temperature of 500° C. or higher for a long time, thereis involved such a problem that the activity of the functional catalystsuch as a denitration catalyst, etc. decreases.

In the method for manufacturing the processing apparatus (10) equippedwith a catalyst-supporting honeycomb structure according to the presentinvention, the corrugated plate-like functional catalyst-containingslurry-applied glass fiber paper peeled off from the die after dryingand the flat plate-like functional catalyst slurry-applied glass fiberpaper after drying are made to have substantially the same size as seenfrom the upper side of the plane.

Thereafter, these are alternately laminated and rendered in a state of ahoneycomb structure, and calcination is conducted in this state, therebyforming the functional catalyst-supporting, flat plate-like glass fiberpaper (3) and the functional catalyst-supporting, corrugated plate-likeglass fiber paper (2).

It is preferable that the calcination step of the corrugated plate-likefunctional catalyst-containing slurry-applied glass fiber paper and theflat plate-like functional catalyst slurry-applied glass fiber paper asrendered in a state of a honeycomb structure is carried out under acondition at from 400 to 550° C. for from 2 to 4 hours.

Here, the functional catalyst slurry-applied, flat plate-like glassfiber paper and the functional catalyst slurry-applied, corrugatedplate-like glass fiber paper are calcinated in a state of beingalternately laminated. This is because if only flat plate-like glassfiber papers are stuck, or only corrugated plate-like glass fiber papersare stuck, followed by calcinating the respective stacks, it might befelt that the bulk decreases, and the calcination efficiency is good;however, uniform calcination cannot be achieved. A space made by theflat plate-like glass fiber paper and the corrugated plate-like glassfiber paper is important for the calcination atmosphere, and accordingto this, uniform calcination can be achieved.

In the packing step of the catalyst-supporting honeycomb structure (1)in the method for manufacturing the processing apparatus (10) equippedwith a catalyst-supporting honeycomb structure according to the presentinvention, it is preferable that the casing (4) is composed of a casingmain body (4 a) having a lateral cross section of a substantiallyU-shape and a flat plate-like lid body (4 b) that covers an opening ofthis, or while illustration is omitted, it is composed of a casing mainbody having a lateral cross section of a substantially L-shape and a lidbody to be opposed to and fitted into this and having a lateral crosssection of a substantially inverted L-shape.

That is, the functional catalyst-supporting, flat plate-like glass fiberpaper (3) after calcination and the functional catalyst-supporting,corrugated plate-like glass fiber paper (2) after calcination arealternately laminated without being bonded to each other, to form thecatalyst-supporting honeycomb structure (1), and thiscatalyst-supporting honeycomb structure (1) is packed in the casing mainbody (4 a) having a lateral cross section of a substantially U-shape,which is made of, for example, stainless steel. Thereafter, thestainless steel-made, flat plate-like lid body (4 b) is fitted andcovered so as to cover the opening of the casing main body (4 a),followed by welding.

Alternatively, the functional catalyst-supporting, flat plate-like glassfiber paper (3) after calcination and the functionalcatalyst-supporting, corrugated plate-like glass fiber paper (2) aftercalcination are alternately laminated without being bonded to eachother, to form the catalyst-supporting honeycomb structure (1), and thiscatalyst-supporting honeycomb structure (1) is packed in a casing mainbody having a lateral cross section of a substantially L-shape, which ismade of, for example, stainless steel. Thereafter, a stainlesssteel-made lid body having a lateral cross section of a substantiallyinverted L-shape is opposed to and fitted into the casing main body,followed by welding.

It is to be noted that in place of welding, it is also possible to fitone end portions of the casing main body (4 a) and of the lid body (4 b)to each other by, for example, mutually connecting them in a loose-pinhinge structure and inserting or removing a pin put into the center ofthe loose-pin hinge structure, thereby fitting the casing main body (4a) and the lid body (4 b) to each other. By fixing the casing main body(4 a) and the lid body (4 b) by utilizing a loose-pin hinge, even if asolid content in the gas to be processed clogs in cells of thecatalyst-supporting honeycomb structure (1), the regeneration processcan be achieved more easily and more rapidly, and hence, such ispreferable.

In the packing step of the catalyst-supporting honeycomb structure (1)in the method for manufacturing the processing apparatus (10) equippedwith a catalyst-supporting honeycomb structure according to the presentinvention, it is preferable that the inorganic fiber blanket (5) is laidon the inner surface of the casing (4) before packing of thecatalyst-supporting honeycomb structure (1).

By laying the inorganic fiber blanket (5) on the inner surface of thecasing (4), a vibration countermeasure can be taken by a frictionalforce by the catalyst-supporting honeycomb structure (1) and theinorganic fiber blanket (5).

Here, in the step of laying the inorganic fiber blanket (5) on the innersurface of the casing (4) and alternately laminating the functionalcatalyst-supporting, flat plate-like glass fiber paper (3) and thefunctional catalyst-supporting, corrugated plate-like glass fiber paper(2) without being bonded to each other, it is preferable that thefunctional catalyst-supporting, flat plate-like glass fiber paper (3) ispacked on the inorganic fiber blanket (5) in the bottom of the casing(4), namely the lowermost stage. Then, the functionalcatalyst-supporting, corrugated plate-like glass fiber paper (2) and thefunctional catalyst-supporting, flat plate-like glass fiber paper (3)are successively alternately laminated. Then, it is preferable that thefunctional catalyst-supporting, flat plate-like glass fiber paper (3) ispacked on the uppermost stage. That is, the number of the flatplate-like glass fiber papers (3) packed in the casing (4) is greaterthan the number of the corrugated plate-like glass fiber papers (2) by1.

It is to be noted that it is also preferable that on inner surfaces ofboth left and right sides of the casing (4), the inorganic fiber blanket(5) is allowed to intervene between the inner surface of the casing (4)and the catalyst-supporting honeycomb structure (1).

In this way, a vibration countermeasure can be taken by a frictionalforce by the catalyst-supporting honeycomb structure (1) and theinorganic fiber blanket (5) on the inner surface of the casing (4).

EXAMPLES

Examples of the present invention are hereunder described, but it shouldnot be construed that the present invention is limited thereto.

Example 1

A denitration catalyst-supporting honeycomb type processing apparatuswas manufactured by the method according to the present invention in thefollowing manner.

First of all, in the method according to the present invention, in astep of baking a commercially available glass fiber paper to remove anorganic binder component contained in the glass fiber paper by burning,as the commercially available glass fiber paper, a glass fiber papercontaining an acrylic resin organic binder was used. The glass fiberpaper was wound in a roll-like form, and a glass fiber paper having alength of 950 mm was cut out from the roll.

Meanwhile, in order to obtain the flat plate-like, denitrationcatalyst-supporting glass fiber paper (3) having not been shaped in acorrugated plate-like form, the same commercially available glass fiberpaper was cut out from the roll; however, a glass fiber paper having alength of 950 mm was cut out from the roll so as to finally have thesame size as that of the corrugated plate-like denitrationcatalyst-supporting glass fiber paper (2) to be packed in the squarecylindrical casing (4) as seen from the upper side of the plane.

It is to be noted that finally, the denitration catalyst-supporting,flat plate-like glass fiber papers (3) and the denitrationcatalyst-supporting, corrugated plate-like glass fiber papers (2) eachconstituting the denitration catalyst-supporting honeycomb structure (1)were cut out in the number of used sheets of 27 and 26, respectivelyfrom the commercially available glass fiber paper roll.

These commercially available glass fiber papers were baked at 400° C.for one hour, thereby removing the organic binder components containedin the glass fibers by burning.

Subsequently, in a step of applying a denitration catalyst-containingslurry on the glass fiber paper after removal of the organic bindercomponent, a denitration catalyst-containing slurry having the followingcomponents was used.

That is, to a slurry of titania fine particles suspended in a silica sol(solid content ratio: 45% by weight, ratio of silica sol to titania:20/80), an ammonium metavanadate powder was added in an amount of 10 gper kg of the slurry, and the whole was stirred for one hour to adsorbammonium metavanadate on titania.

This denitration catalyst-containing slurry was applied on a surface ofeach of the glass fiber papers after removal of the above-describedorganic binder component in a applying amount of 1,200 g/m² on acorrugated plate-like shaping die.

When the above-described denitration catalyst-containing slurry wasapplied on the organic binder component-removed glass fiber paper afterbaking, an inorganic binder composed of the silica sol contained in theslurry carried out a function as a binder of the glass fiber paper.Thus, by applying the denitration catalyst-containing slurry on theglass fiber paper after baking, it became possible to keep thecorrugated shape.

That is, in a shaping step of the denitration catalyst-containingslurry-applied glass fiber paper in a corrugated plate-like form, a diecomposed of a stainless steel-made corrugated plate-like panel havingparallel recessed grooves having a width of 10.4 mm, a height of 7.4 mm,and a radius of curvature in a groove bottom of 1.6 mm was used, thedenitration catalyst-containing slurry-applied glass fiber paper placedon the die was pressed down along the recessed grooves of the die by apressing jig, thereby achieving shaping. Though it is preferable to use,as the pressing jig, a jig in which a portion that comes into contactwith the glass fiber paper is subjected to water repellent finishing,namely TEFLON (registered trademark) finishing, in this Example, aTEFLON (registered trademark) plate having a side edge portion cominginto the recessed grooves of the die composed of a corrugated plate-likepanel was used.

It is to be noted that a applying work of the denitrationcatalyst-containing slurry on the surface of the flat plate-like organicbinder-removed glass fiber paper to be not shaped can be conducted on,for example, a stainless steel-made flat plate-like panel.

Subsequently, a drying step of the shaped, corrugated plate-like,denitration catalyst-containing slurry-applied glass fiber paper and adrying step of the flat plate-like, denitration catalyst slurry-appliedglass fiber paper having not been shaped in a corrugated plate-like formwere carried out at a temperature of 300° C. for one hour, respectively.

The corrugated plate-like, denitration catalyst-containingslurry-applied glass fiber paper after drying was peeled off from thedie composed of a corrugated plate-like panel.

The corrugated plate-like, denitration catalyst-containingslurry-applied glass fiber paper peeled off from the die after dryingand the flat plate-like, denitration catalyst slurry-applied glass fiberpaper after drying are of a rectangle of the same size as seen from theupper side of the plane and have a width of 142 mm and a length of 950mm, respectively.

27 sheets of the flat plate-like, denitration catalyst slurry-appliedglass fiber papers after drying and 26 sheets of the corrugatedplate-like, denitration catalyst-containing slurry-applied glass fiberpapers after drying were alternately laminated and rendered in a stateof a honeycomb structure. Calcination was conducted in this state at400° C. for one hour, thereby forming the denitrationcatalyst-supporting, flat plate-like glass fiber paper (3) and thedenitration catalyst-supporting, corrugated plate-like glass fiber paper(2).

At that time, a space made by the flat plate-like, denitration catalystslurry-applied glass fiber paper and the corrugated plate-like,denitration catalyst slurry-applied glass fiber paper is important forthe calcination atmosphere, and according to this, uniform calcinationcould be achieved.

Subsequently, the square cylindrical casing (4) composed of thestainless steel-made casing main body (4 a) having a lateral crosssection of a substantially U-shape and the flat plate-like, stainlesssteel-made lid body (4 b) that covers an opening of this was provided;the ceramic fiber-made blanket (5) was laid in the casing main body (4a); and thereafter, the catalyst-supporting honeycomb structure (1) inwhich the denitration catalyst-supporting, flat plate-like glass fiberpaper (3) after calcination and the denitration catalyst-supporting,corrugated plate-like glass fiber paper (2) after calcination werealternately laminated without being bonded to each other was packed,thereby manufacturing the denitration catalyst-supporting honeycomb typeprocessing apparatus (10) according to the present invention.

According to the processing apparatus (10) equipped with acatalyst-supporting honeycomb structure of Example 1 of the presentinvention, the catalyst-supporting honeycomb structure (1) could beformed by using a commercially available, inexpensive glass fiber paperas a base material. Moreover, since it is merely required that afunctional catalyst-containing slurry is applied on the glass fiberpaper after removal of the organic binder component and then dried andcalcinated, the manufacturing cost is low without requiring large-scaleequipment such as a dipping tank, a drying device, etc. asconventionally used for a so-called adhesive type honeycomb structure.

In addition, for example, in an exhaust gas cleaning process or thelike, even if a solid content in a gas to be processed clogs in cells ofthe catalyst-supporting honeycomb structure (1) with a lapse ofoperating time, since the functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) and the functional catalyst-supporting,flat plate-like glass fiber paper (3) are alternately laminated withoutbeing bonded to each other, to form the catalyst-supporting honeycombstructure (1), and this catalyst-supporting honeycomb structure (1) ispacked in the casing (4), these can be discharged separately from thecasing (4), the discharged functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) and the functional catalyst-supporting,flat plate-like glass fiber paper (3) as discharged can be easilyregenerated by means of cleaning or the like. Therefore, a lowering of acontact area with the gas to be processed or an increase of a pressureloss can be surely prevented from occurring.

Example 2

Though the denitration catalyst-supporting honeycomb type processingapparatus (10) is manufactured by the method according to the presentinvention in the same manner as that in the case of the above-describedExample 1, a point which is different from that in the case of theabove-described Example 1 resides in components of the denitrationcatalyst-containing slurry.

That is, to a slurry of titania fine particles suspended in a silica sol(solid content ratio: 45% by weight, ratio of silica to titania: 20/80),an ammonium metavanadate powder was added in an amount of 10 g per kg ofthe slurry, and the whole was stirred for one hour to adsorb ammoniummetavanadate on titania.

Subsequently, to the above-described slurry, an ammonium metatungstateaqueous solution (3.88 moles/L) was further added in an amount of 28 mLper kg of the slurry, and the whole was stirred for one hour.

The denitration catalyst-supporting honeycomb type processing apparatus(10) was manufactured in the same manner as that in the case of theabove-described Example 1, except for using this denitrationcatalyst-containing slurry.

Similar to the case of the above-described Example 1, according to theprocessing apparatus (10) equipped with a catalyst-supporting honeycombstructure of Example 2 of the present invention, the catalyst-supportinghoneycomb structure (1) could be formed by using a commerciallyavailable, inexpensive glass fiber paper as a base material. Moreover,since it is merely required that a functional catalyst-containing slurryis applied on the glass fiber paper after removal of the organic bindercomponent and then dried and calcinated, the manufacturing cost is lowwithout requiring large-scale equipment such as a dipping tank, a dryingdevice, etc. as conventionally used for a so-called adhesive typehoneycomb structure.

In addition, for example, in an exhaust gas cleaning process or thelike, even if a solid content in a gas to be processed clogs in cells ofthe catalyst-supporting honeycomb structure (1) with a lapse ofoperating time, since the functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) and the functional catalyst-supporting,flat plate-like glass fiber paper (3) are alternately laminated withoutbeing bonded to each other, to form the catalyst-supporting honeycombstructure (1), and this catalyst-supporting honeycomb structure (1) ispacked in the casing (4), these can be discharged separately from thecasing (4), the discharged functional catalyst-supporting, corrugatedplate-like glass fiber paper (2) and the functional catalyst-supporting,flat plate-like glass fiber paper (3) as discharged can be easilyregenerated by means of cleaning or the like. Therefore, a lowering of acontact area with the gas to be processed or an increase of a pressureloss can be surely prevented from occurring.

The invention claimed is:
 1. A processing apparatus equipped with afunctional catalyst, wherein the functional catalyst comprises acatalyst-supporting honeycomb structure in a casing, wherein thecatalyst-supporting honeycomb structure in a casing comprises: acorrugated plate-like glass fiber paper having a functional catalystsupported thereon, a flat plate-like glass fiber paper having the samefunctional catalyst supported thereon, and an inorganic fiber blanketlaid on an inner surface of the casing; wherein the corrugatedplate-like glass fiber paper and the flat plate-like glass fiber paperare alternately laminated without being bonded to each other, to form acatalyst-supporting honeycomb structure, and the catalyst-supportinghoneycomb structure is packed in the inorganic fiber blanket in thecasing.
 2. The processing apparatus equipped with a functional catalystaccording to claim 1, wherein the casing has a square cylindrical shape,and the casing is composed of a casing main body having a lateral crosssection of a substantially U-shape and a flat plate-like lid body thatcovers an opening of this, or composed of a casing main body having alateral cross section of a substantially L-shape and a lid body to befitted into this and having a lateral cross section of a substantiallyinverted L-shape.
 3. The processing apparatus equipped with a functionalcatalyst according to claim 1, wherein the functional catalyst is acatalyst selected from the group consisting of a denitration catalyst, adesulfurization catalyst, a dioxin decomposition catalyst, and anammonia decomposition catalyst, and is used for an exhaust gas cleaningprocess or manufacture of hydrogen by ammonia decomposition.
 4. Theprocessing apparatus equipped with a functional catalyst according toclaim 2, wherein the functional catalyst is a catalyst selected from thegroup consisting of a denitration catalyst, a desulfurization catalyst,a dioxin decomposition catalyst, and an ammonia decomposition catalyst,and is used for an exhaust gas cleaning process or manufacture ofhydrogen by ammonia decomposition.
 5. The processing apparatus equippedwith a functional catalyst according to claim 1, wherein the functionalcatalyst is supported on the corrugated plate-like glass fiber paper andthe flat plate-like glass fiber paper by applying a functionalcatalyst-containing slurry comprising 10 to 30% by weight of silica solto the corrugated plate-like glass fiber paper and the flat plate-likeglass fiber paper.